The Complexation between hexadecyl- and dodecyltrimethylainmonium bromides (CTAB and DTAB) with sodium poly[(vinyl alcohol)-co-(vinyl sulfate)] (PVAS) copolymer of low charge density has been investigated using pyrene fluorescence spectroscopy, electrophoretic mobility, turbidity, and dynamic light scattering measurements. The results indicate that the binding of the cationic surfactant occurs in three steps. At low surfactant concentrations, the cationic amphiphile binds to the vinyl sulfate groups. Above charge neutralization, surfactant binding may occur on the surface of the hydrophobic vinyl sulfate/C TAB nano assemblies. At even higher concentrations, the surfactant binds ion the nonionic vinyl alcohol units of the polyion which reswells the PVAS/C(n)TAB complexes and makes them highly soluble in water. In earlier. studies On oppositely Charged ionic surfactants and homopolyelectrolytes the impact of mixing protocols was found remarkable, especially at surfactant excess, where these systems can be trapped in the charge stabilized colloidal dispersion state. In contrast, in the cage of PVAS/C TAB mixtures the effect of mixing is less pronounced and diminishes with increasing ionic strength or decreasing alkyl chain length of the surfactant. These findings are rationalized by taking into account the different binding mechanism of surfactants on Oppositely charged homopolyelectrolytes and double hydrophilic copolymers.